Gas-Phase Ozone Oxidation of Monoterpenes: Gaseous and ...

GAS-PHASE OZONE OXIDATION OF MONOTERPENES 221
Further differentiation among the three isomers is impossible on the basis of CI and
EI mass spectra. Figure 2-P 6 shows ion fragment patters using pinalic-4-acid as an
example. Compound P 7 is identified as cis-pinonic acid, and the identification has
been confirmed by comparison with an authentic standard. The CI mass spectrum
of its derivative is shown in Figure 2-P 7 . Compound P 8 is tentatively identified
as hydroxy norpinonic acid, with a MW of 525 for its derivative (Figure 2-P 8 ).
Compound P 9 is tentatively identified as hydroxy pinonic acid, with a MW of 539
for its derivative (Figure 2-P 9 ).
Some of the products observed here have been reported in previous studies.
Nopinone has long been identified as a major product in the β-pinene/O 3 reaction
(Hull, 1981; Hatakeyama et al., 1989; Grosjean et al., 1993, Hakola et
al., 1994). Using GC/MS and nuclear magnetic resonance (NMR) analyses, Hull
also positively identified 3-hydroxy-pina ketone and 3-oxo-pina ketone and had
indirect evidence for the formation of 1-hydroxy-pina ketone. Products that are
reported here for the first time include pinic acid, norpinic acid, 2,2,-dimethyl-3-
formyl-cyclobutyl methanoic acid, norpinonic acid and its isomers, pinonic acid,
hydroxy norpinonic acid, hydroxy pinonic acid, and 2,2-dimethyl-cyclobutane-1,3-
dicarboxaldehyde.
3.2. PRODUCTS FROM OZONE OXIDATION OF SABINENE
Carbonyl bearing products of the sabinene/O 3 reaction are shown in Figure 3(a),
and OH/COOH bearing products are shown in Figure 3(b). Table V lists the MWs
and chemical structures of these products. Most products are analogous to those
identified in the β-pinene/O 3 reaction, and their methane CI mass spectra are similar
to those in the β-pinene/O 3 reaction. The CI mass spectra are given only for
the products unique in the sabinene/O 3 reaction (Figure 4). Interested readers can
get from us the mass spectra data for those analogous products.
Among the products, compound S 1 ,S 2 ,andS 3 contain only OH/COOH groups
(type 2 compounds). Compound S 1 is tentatively identified as norsabinic acid on
the basis of that it shows a MW of 316 for its derivative, and elutes at an earlier retention
time than that of norpinic acid. The CI spectrum of compound S 2 indicates a
MW of 330 for its TMS derivative. S 2 elutes from the GC column earlier than pinic
acid. It is tentatively identified as sabinic acid, the analogue of pinic acid derived
from sabinene. Compound S 3 is pinic acid, confirmed by authentic standard. The